Light emitting material, manufacture method thereof and organic light emitting diode using the light emitting material

ABSTRACT

An organic light emitting diode includes a light emitting layer that includes a light emitting material of the constitutional formulaThe structure is unitary, and the formula weight is determined, and the better solubility and film formation are provided, and the thin film status is stable; it possesses a very high decomposition temperature and a lower sublimation temperature, and is easy to sublime to be light emitting material of high purity, and can be applied for small molecule organic light emitting diode. In the method for manufacturing the light emitting material, p-bromothiophenol and 4-Bromo-2-fluorobenzonitrile are employed to be starting materials, and an intermediate of the light emitting material is obtained with a series of simple reactions, and finally, the light emitting material is obtained with Ullmann reaction or Suzuki reaction, and these steps are simple and the production is high.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a divisional application of co-pending U.S. patent applicationSer. No. 16/278,720, filed on Feb. 19, 2019, which is a divisionalapplication of U.S. patent application Ser. No. 15/122,410, filed onAug. 30, 2016 and now U.S. Pat. No. 10,280,365, which is a nationalstage of PCT Application No. PCT/CN2016/095615, filed on Aug. 17, 2016,claiming foreign priority of Chinese Patent Application No.201610579646.9, filed on Jul. 20, 2016.

FIELD OF THE INVENTION

The present invention relates to a display technology field, and moreparticularly to a light emitting material, a manufacture method thereofand an organic light emitting diode using the light emitting material.

BACKGROUND OF THE INVENTION

The OLED (Organic Light-Emitting Diode) display, which is also named asthe Organic light emitting display, is a new flat panel display device.Because it possesses advantages of simple manufacture process, low cost,low power consumption, high light emitting brightness, wide operatingtemperature range, thin volume, fast response speed, and being easy toachieve the color display and the large screen display, and being easyto achieve the match with the integrated circuit driver, and being easyto achieve the flexible display. Therefore, it has the broad applicationprospects.

The OLED display utilizes the organic light emitting diode for lightemission. Thus, it is extremely important to improve the efficiency andlifetime of the organic light emitting diode. Now, the organic lightemitting diode has already made considerable progress. With thefluorescence phosphorescence hybrid, the white light element with thesimple structure and high efficiency can be obtained. The efficiency ofsuch fluorescence phosphorescence hybrid element significantly relies onthe efficiency of the fluorescence. Therefore, it still has vitalsignificant meaning to develop the high efficiency fluorescencematerial.

In comparison with polymer, the small molecule light emitting moleculehas the simple steps, the stable structure and can be purified, and thenthe higher element efficiency can be obtained for the possiblecommercial application. The method of manufacturing multiple layerelement by implementing evaporation or solution process with smallmolecule has already drawn the great attention and the great progresshas been made. However, the traditional organic fluorescence materialonly can utilize 25% of singlet excitons. Thus, there is extreme bigrestriction to the efficiency of the element. Recently, the JapaneseAdachi research group utilizes the thermally activated delayedfluorescence mechanism to make the exciton availability of all organicmaterial reach up to 100%, and the organic fluorescence elementefficiency progresses significantly. Nevertheless, there is few for suchkind of materials. Therefore, the type expansion for such kind ofmaterial has the significant meaning for the application in the future.For now, the organic small molecule light emitting material of simplestructure, and possessing well performance and satisfying thecommercialization requirement is still so limited. It is still profoundto develop the light emitting material of low cost and excellentefficiency.

SUMMARY OF THE INVENTION

An objective of the present invention is to provide a light emittingmaterial, in which the structure is unitary, and the formula weight isdetermined, and the better solubility and film formation are provided tobe applied for small molecule organic light emitting diode.

Another objective of the present invention is to provide a manufacturemethod of the light emitting material, in which the steps are simple,and the production is high.

Another objective of the present invention is to provide an organiclight emitting diode, in which the light emitting layer comprises theaforesaid light emitting material that has higher light emissionefficiency and stability.

For realizing the aforesaid objectives, the present invention firstprovides a light emitting material, in which a constitutional formula is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Ar₁ and Ar₂ are the same.

The light emitting material comprises one or more of followingcompounds:

The present invention further provides a manufacture method of lightemitting material, comprising steps of:

step 1, manufacturing an intermediate

step 2, obtaining light emitting material with Ullmann reaction orSuzuki reaction of the intermediate

and an aromatic amine compound, in which a constitutional formula of thelight emitting material is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Ar₁ and Ar₂ are the same.

The light emitting material comprises one or more of followingcompounds:

The step 1 comprises:

step 11, obtaining

with a reaction of p-bromothiophenol and 4-Bromo-2-fluorobenzonitrile;

step 12, hydrolyzing

in an alkaline condition, and acidizing the same to obtain

step 13, generating dehydration condensation reaction to

to obtain

step 14, obtaining the intermediate

with a reaction of

and hydrogen peroxide.

The present invention provides an organic light emitting diode,comprising a substrate, and an anode, a Hole Injection Layer, a HoleTransporting Layer, a light emitting layer, an Electron Transport Layer,an Electron Injection Layer and a cathode stacking up on the substratefrom bottom to top in order;

the light emitting layer comprises light emitting material, in which aconstitutional formula is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Ar₁ and Ar₂ are the same.

The light emitting material comprises one or more of followingcompounds:

The benefits of the present invention are: the present inventionprovides a light emitting material, in which the structure is unitary,and the formula weight is determined, and the better solubility and filmformation are provided, and the thin film status is stable; it possessesa very high decomposition temperature and a lower sublimationtemperature, and is easy to sublime to be light emitting material ofhigh purity, and can be applied for small molecule organic lightemitting diode; by changing the aromatic amine group, which isconnected, the physical property can be improved in advance to promotethe performance of the photoelectric element of the light emittingmaterial. The present invention provides a manufacture method of thelight emitting material. p-bromothiophenol and4-Bromo-2-fluorobenzonitrile are employed to be starting materials, andthe intermediate of the light emitting material is obtained with aseries of simple reactions, and finally, the light emitting material isobtained with Ullmann reaction or Suzuki reaction, and the steps aresimple and the production is high. The present invention provides anorganic light emitting diode, in which the light emitting layercomprises the aforesaid light emitting material that has higher lightemission efficiency and stability.

In order to better understand the characteristics and technical aspectof the invention, please refer to the following detailed description ofthe present invention is concerned with the diagrams, however, providereference to the accompanying drawings and description only and is notintended to be limiting of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The technical solution and the beneficial effects of the presentinvention are best understood from the following detailed descriptionwith reference to the accompanying figures and embodiments.

In drawings,

FIG. 1 is a flowchart of a manufacture method of light emitting materialaccording to the present invention;

FIG. 2 is a structure diagram of an organic light emitting diodeaccording to the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

For better explaining the technical solution and the effect of thepresent invention, the present invention will be further described indetail with the accompanying drawings and the specific embodiments.

The present invention first provides a light emitting material, in whicha constitutional formula is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Preferably, Ar₁ and Ar₂ are the same.

Specifically, the light emitting material comprises one or more offollowing compounds:

In the aforesaid light emitting material, the structure is unitary, andthe formula weight is determined, and the better solubility and filmformation are provided, and the thin film status is stable; it possessesa very high decomposition temperature and a lower sublimationtemperature, and is easy to sublime to be light emitting material ofhigh purity, and can be applied for small molecule organic lightemitting diode; by changing the aromatic amine group, which isconnected, the physical property can be improved in advance to promotethe performance of the photoelectric element of the light emittingmaterial.

Please refer to FIG. 1. The present invention further provides amanufacture method of light emitting material, comprising steps of:

step 1, manufacturing an intermediate

A synthetic route of the intermediate

is:

Specifically, the step 1 comprises steps of:

step 11, obtaining

with a reaction of p-bromothiophenol and 4-Bromo-2-fluorobenzonitrile.

The specific implementing steps of the step 11 are:

In 250 ml boiling flask-3-neck, 0.73 g (30 mmol) NaH is slowly added in20 ml dry dimethylformamide (DMF) dissolved with 4.6 g (25 mmol)p-bromothiophenol, and then 20 ml dry dimethylformamide dissolved with 5g (25 mmol) 4-Bromo-2-fluorobenzonitrile is dropped into it. Under theprotection of nitrogen, 20 h heating reflux reaction is implemented, andthe temperature drops to the room temperature after the reaction iscompleted, and then the reaction fluid is poured in 50 ml 1M NaOHsolution, and extracted in dichloromethane (DCM) to be decompressed toremove the solvent, and through silicagel column, white color solid 5.2g, i.e. the compound b1 is obtained. Molecular formula: C₁₃H₇Br₂NS, andMS: 366.87, and elemental analysis: C, 42.31; H, 1.91; Br, 43.30; N,3.80; S, 8.69.

step 12, hydrolyzing

in an alkaline condition, and acidizing the same to obtain

The specific implementing steps of the step 12 are:

In 250 ml boiling flask-3-neck, 80 ml deionized water, 15 g KOH and 80ml alcohol are added, and 5.2 g compound b1 is added in reaction bottleto reflow overnight under protection of nitrogen. After the reaction iscompleted, the reaction solution is cooled to the room temperature, andadded in 100 ml 6M hydrochloric acid, the white solid is separated outwith ice bath, and extracted and filtered, and then dried to obtainwhite solid 5.1 g, i.e. the compound b2. Molecular formula: C₁₃H₈Br₂O₂S,and MS: 385.86, and elemental analysis: C, 40.23; H, 2.08; Br, 41.18; O,8.25; S, 8.26.

step 13, generating dehydration condensation reaction to

to obtain

The specific implementing steps of the step 13 are:

In 500 ml boiling flask, 2.75 g (10 mmol) compound b2 is added, and 500ml chloroform is added to be solvent, and 3.2 g (20 mmol, 2 equ)trifluoroacetic anhydride is dropped, and stirred 10 min in the roomtemperature, and then 0.5 g Boron trifluoride etherate is added, and theice bath is removed for reacting 12 h at the room temperature. After thereaction is completed, sodium sulfite saturated aqueous solution isadded to quench redundant trifluoroacetic anhydride, and separated, andreduced pressure distilled to remove the solvent, and through column,

is obtained. Molecular formula: C₁₃H₈Br₂O₂S; MS: 385.86; elementalanalysis: C, 40.23; H, 2.08; Br, 41.18; O, 8.25; S, 8.26.

step 14, obtaining the intermediate

with a reaction of

and hydrogen peroxide.

The specific implementing steps of the step 14 are:

In 250 ml boiling flask-3-neck, 5 g (13.59 mmol), 50 mL dichloromethane

20 mL ethylic acid, 3 mL (5 equ) hydrogen peroxide are added. Thereaction last 8 hours at 80° C., and the temperature is lowered afterthe reaction is completed, and water is used to remove redundanthydrogen peroxide for extraction. Through column, 4.6 g intermediate

is obtained, and productivity is 85%. Molecular formula: C₁₃H₆Br₂O₃S;M/Z=399.84; theoretic value: 402.06; elemental analysis: 401.84(100.0%), 399.84 (50.0%), 403.84 (48.1%), 402.84 (15.0%), 404.84 (7.8%),400.84 (7.5%), 403.83 (4.4%), 405.83 (2.2%).

step 2, obtaining light emitting material with Ullmann reaction orSuzuki reaction of the intermediate

and an aromatic amine compound, in which a constitutional formula of thelight emitting material is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Preferably, Ar₁ and Ar₂ are the same.

Specifically, the light emitting material comprises one or more offollowing compounds:

Specifically, in the step 2, the aromatic amine compound comprises oneor more of carbazol, diphenylamine, 9,9-diMethylacridan,4-carbazoleBenzene borate ester, 4-phenylcarbazole borate ester,4-triphenylamine borate ester, 4-phenylthiophene-S,S-dioxide borateester;

a constitutional formula of the carbazol is

a constitutional formula of the diphenylamine is

a constitutional formula of the 9,9-diMethylacridan is

a constitutional formula of the 4-carbazoleBenzene borate ester is

a constitutional formula of the 4-phenylcarbazole borate ester is

a constitutional formula of the 4-triphenylamine borate ester is

a constitutional formula of the 4-phenylthiophene-S,S-dioxide borateester is

The specific implementing method of the step 2 is described below indetail with combination of the specific embodiment.

Embodiment 1:

is obtained with Ullmann reaction of intermediate

and carbazol, and the reaction formula is:

The specific implementing steps are:

Under the protection of nitrogen, in boiling flask-3-neck, 100 mlmethylbenzene, 0.72 g (2 mmol) intermediate

0.67 g (4 mmol) carbazol are added, and 0.3 g sodium tert-butoxide isadded in stirring, and then 20 mg tris(dibenzylideneacetone)dipalladium(Pd2(dba)3) is added, and then 0.3 ml 10% tri-tert-butylphosphine hexanesolution is added, and heated reflux to react overnight. The temperatureis lowered, and extracted in dichloromethane in organic phase, and spindried, and through column. White color solid product 0.81 g is obtained,and productivity is 75%. Molecular formula: C₃₇H₂₂N₂O₃S; M/S=574.14;theoretic value: 574.65; elemental analysis: 574.14 (100.0%), 575.14(40.4%), 576.14 (9.2%), 576.13 (4.5%), 577.13 (1.8%), 575.13 (1.5%),577.15 (1.0%).

Embodiment 2:

is obtained with Ullmann reaction of intermediate

and diphenylamine, and the reaction formula is:

The specific implementing steps are:

Under the protection of nitrogen, in boiling flask-3-neck, 100 mlmethylbenzene, 0.72 g (2 mmol) intermediate

0.84 g (4 mmol) diphenylamine are added, and 0.3 g sodium tert-butoxideis added in stirring, and then 20 mgtris(dibenzylideneacetone)dipalladium (Pd2(dba)3) is added, and then 0.3ml 10% tri-tert-butylphosphine hexane solution is added, and heatedreflux to react overnight. The temperature is lowered, and extracted indichloromethane in organic phase, and spin dried, and through column.White color solid product 0.81 g is obtained, and productivity is 75%.Molecular formula: C₃₇H₂₆N₂O₃S; M/S=578.17; theoretic value: 578.68;elemental analysis: 578.17 (100.0%), 579.17 (41.2%), 580.17 (9.1%),580.16 (4.5%), 581.17 (2.2%), 581.18 (1.0%).

Embodiment 3:

is obtained with Ullmann reaction of intermediate

and 9,9-diMethylacridan, and the reaction formula is:

The specific implementing steps are:

Under the protection of nitrogen, in boiling flask-3-neck, 100 mlmethylbenzene, 0.72 g (2 mmol) intermediate

0.84 g (4 mmol) 9,9-diMethylacridan are added, and 0.3 g sodiumtert-butoxide is added in stirring, and then 20 mgtris(dibenzylideneacetone)dipalladium (Pd2(dba)3) is added, and then 0.3ml 10% tri-tert-butylphosphine hexane solution is added, and heatedreflux to react overnight. The temperature is lowered, and extracted indichloromethane in organic phase, and spin dried, and through column.White color solid product 0.85 g is obtained, and productivity is 79%.Molecular formula: C₄₃H₃₄N₂O₃S; M/S=658.23; theoretic value: 658.81;elemental analysis: 658.23 (100.0%), 659.23 (48.2%), 660.24 (10.8%),660.22 (4.5%), 661.23 (2.2%), 661.24 (2.0%), 660.23 (1.3%).

Embodiment 4:

is obtained with Suzuki reaction of intermediate

and 4-carbazoleBenzene borate ester, and the reaction formula is:

The specific implementing steps are:

Under the atmosphere of nitrogen, in 250 ml boiling flask, 96 mlmethylbenzene, 32 ml alcohol, 16 ml 2M potassium carbonate aqueoussolution, 0.72 g (2 mmol) intermediate

2.06 g (1.2 equ) 4-carbazoleBenzene borate ester are added, and stirredat the room temperature, and then 100 mg triphenylphosphineplatinum(catalyzer) is added and 96° C. reflows for 24 hours. It is cooled tothe room temperature, and extracted in dichloromethane, and dried inanhydrous magnesium sulfate. White color solid product 0.86 g isobtained, and productivity is 79%. Molecular formula: C₄₉H₃₀N₂O₃S;M/S=726.2; theoretic value: 726.84; elemental analysis: 726.20 (100.0%),727.20 (54.3%), 728.20 (15.2%), 728.19 (4.5%), 729.21 (2.7%), 729.20(2.6%).

Embodiment 5:

is obtained with Suzuki reaction of intermediate

and 4-phenylcarbazole borate ester, and the reaction formula is:

The specific implementing steps are:

Under the atmosphere of nitrogen, in 250 ml boiling flask, 96 mlmethylbenzene, 32 ml alcohol, 16 ml 2M potassium carbonate aqueoussolution, 0.72 g (2 mmol) intermediate

2.32 g (1.2 equ) 4-phenylcarbazole borate ester are added, and stirredat the room temperature, and then 100 mg triphenylphosphineplatinum(catalyzer) is added and 96° C. reflows for 24 hours. It is cooled tothe room temperature, and extracted in dichloromethane, and dried inanhydrous magnesium sulfate. White color solid product 0.92 g isobtained, and productivity is 83%. Molecular formula: C₄₉H₃₀N₂O₃S;M/S=726.2; theoretic value: 726.84; elemental analysis: 726.20 (100.0%),727.20 (54.3%), 728.20 (15.2%), 728.19 (4.5%), 729.21 (2.7%), 729.20(2.6%).

Embodiment 6:

is obtained with Suzuki reaction of intermediate

and 4-triphenylamine borate ester, and the reaction formula is:

The specific implementing steps are:

Under the atmosphere of nitrogen, in 250 ml boiling flask, 96 mlmethylbenzene, 32 ml alcohol, 16 ml 2M potassium carbonate aqueoussolution, 0.72 g (2 mmol) intermediate

2.32 g (1.2 equ) 4-triphenylamine borate ester are added, and stirred atthe room temperature, and then 100 mg triphenylphosphineplatinum(catalyzer) is added and 96° C. reflows for 24 hours. It is cooled tothe room temperature, and extracted in dichloromethane, and dried inanhydrous magnesium sulfate. White color solid product 0.96 g isobtained, and productivity is 87%. Molecular formula: C₄₉H₃₄N₂O₃S;M/S=730.23; theoretic value: 730.87; elemental analysis: 730.23(100.0%), 731.23 (54.7%), 732.24 (14.0%), 732.22 (4.5%), 733.24 (2.8%),733.23 (2.5%), 732.23 (1.4%).

Embodiment 7:

is obtained with Suzuki reaction of intermediate

and 4-phenylthiophene-S,S-dioxide borate ester, and the reaction formulais:

The specific implementing steps are:

Under the atmosphere of nitrogen, in 250 ml boiling flask, 96 mlmethylbenzene, 32 ml alcohol, 16 ml 2M potassium carbonate aqueoussolution, 0.72 g (2 mmol) intermediate

2.06 g (1.2 equ) 4-phenylthiophene-S,S-dioxide borate ester are added,and stirred at the room temperature, and then 100 mgtriphenylphosphineplatinum (catalyzer) is added and 96° C. reflows for24 hours. It is cooled to the room temperature, and extracted indichloromethane, and dried in anhydrous magnesium sulfate. White colorsolid product 0.96 g is obtained, and productivity is 87%. Molecularformula: C₄₉H₃₀N₂O₇S₃; M/S=854.12; theoretic value: 854.97; elementalanalysis: 854.12 (100.0%), 855.12 (56.1%), 856.13 (15.5%), 856.12(15.3%), 857.12 (7.5%), 857.13 (3.7%), 858.12 (2.3%).

In the aforesaid manufacture method of the light emitting material,p-bromothiophenol and 4-Bromo-2-fluorobenzonitrile are employed to bestarting materials, and the intermediate of the light emitting materialis obtained with a series of simple reactions, and finally, the lightemitting material is obtained with Ullmann reaction or Suzuki reaction,and the steps are simple and the production is high.

Please refer to FIG. 2. The present invention further provides anorganic light emitting diode, comprising a substrate 10, and an anode20, a Hole Injection Layer 30, a Hole Transporting Layer 40, a lightemitting layer 50, an Electron Transport Layer 60, an Electron InjectionLayer 70 and a cathode 80 stacking up on the substrate 10 from bottom totop in order;

the light emitting layer 50 comprises light emitting material, in whicha constitutional formula is

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groupsshown in formula (1), formula (2), formula (3), formula (4), formula(5), formula (6), formula (7);

Preferably, Ar₁ and Ar₂ are the same.

Specifically, the light emitting material comprises one or more offollowing compounds:

Preferably, in material of the light emitting layer 50, a masspercentage of the light emitting material is 1%.

Specifically, the light emitting layer 50 can emit red light, yellowlight, green light or blue light.

Specifically, material of the anode 20 comprises transparent metaloxide. The transparent metal oxide is preferably to be Indium Tin Oxide(ITO).

Specifically, material of the Hole Injection Layer 30 comprises2,3,6,7,10,11-Hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN), and aconstitutional formula of the2,3,6,7,10,11-Hexacyano-1,4,5,8,9,12-hexaazatriphenylene is.

Specifically, material of the Hole Transporting Layer 40 comprises1,1-Bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane (TAPC), and aconstitutional formula of the1,1-Bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane is

Specifically, material of the light emitting layer 50 further comprises4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP), and a constitutional formulaof the 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl is

Specifically, material of the Electron Transport Layer 60 comprises1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (TmPyPB), and a constitutionalformula of the 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene is

Specifically, material of the Electron Injection Layer 70 comprisesLithium fluoride (LiF).

Specifically, material of cathode 80 comprises aluminum (Al).

Preferably, a thickness of the anode 20 is 95 mm, and a thickness of theHole Injection Layer 30 is 5 mm, and a thickness of the HoleTransporting Layer 40 is 20 mm, and a thickness of the light emittinglayer 50 is 35 mm, and a thickness of the Electron Transport Layer 60 is55 mm, and a thickness of the Electron Injection Layer 70 is 1 mm, and athickness of the cathode 80 is larger than 80 nm.

The manufacture process of the organic light emitting diode is: puttingIndium Tin Oxide transparent conductive glass in the cleaner for theultrasonic process, and using the deionized water for cleaning to employultrasound to remove oil in the mixture solution of acetone/ethanol, andthen, baking the same in the clean environment until the water iscompletely removed, and then, using ultraviolet light and ozone forcleaning, and employing low energy cation to bombard the same to obtainthe anode 20, and putting the transparent conductive glass with theanode 20 in the vacuum chamber, and vacuuming to 1×10⁻⁵-9×10⁻³ Pa, andnext, sequentially evaporating the Hole Injection Layer 30, the HoleTransporting Layer 40, the plurality of light emitting layer 50, theElectron Transport Layer 60, the Electron Injection Layer 70 and thecathode 80 on the anode 20, and ultimately obtaining the organic lightemitting diode of this embodiment.

In conclusion, the present invention provides a light emitting material,in which the structure is unitary, and the formula weight is determined,and the better solubility and film formation are provided, and the thinfilm status is stable; it possesses a very high decompositiontemperature and a lower sublimation temperature, and is easy to sublimeto be light emitting material of high purity, and can be applied forsmall molecule organic light emitting diode; by changing the aromaticamine group, which is connected, the physical property can be improvedin advance to promote the performance of the photoelectric element ofthe light emitting material. The present invention provides amanufacture method of the light emitting material. p-bromothiophenol and4-Bromo-2-fluorobenzonitrile are employed to be starting materials, andthe intermediate of the light emitting material is obtained with aseries of simple reactions, and finally, the light emitting material isobtained with Ullmann reaction or Suzuki reaction, and the steps aresimple and the production is high. The present invention provides anorganic light emitting diode, in which the light emitting layercomprises the aforesaid light emitting material that has higher lightemission efficiency and stability.

Above are only specific embodiments of the present invention, the scopeof the present invention is not limited to this, and to any persons whoare skilled in the art, change or replacement which is easily derivedshould be covered by the protected scope of the invention. Thus, theprotected scope of the invention should go by the subject claims.

What is claimed is:
 1. An organic light emitting diode, comprising a substrate, an anode, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode stacked in sequence on the substrate from bottom to top; wherein the light emitting layer comprises a light emitting material having the following constitutional formula:

wherein Ar₁ and Ar₂ are respectively selected from aromatic amine groups shown in formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7);

and wherein the light emitting material is selected from following compound: 